DE19651686A1 - New substituted phenylketoenols - Google Patents

Abstract

This invention concerns new phenyl-substituted cyclic ketoenols of formula (I) in which Het stand for one of the groups (1), (2) or (3), and G, V, W, Y, and Z have the meaning given in the description, processes and intermediate products for their production and their us as pesticides and herbicides.

Description

The invention relates to novel phenyl-substituted cyclic ketoenols, several processes and intermediates for their manufacture and their use as pests pesticides and herbicides.

It has already been known that certain phenyl-substituted cyclic keto enols are effective as insecticides, acaricides and / or herbicides.

1H-Arylpyrrolidinedione derivatives are known (EP-A-456 063, EP-A-521 334, EP-A- 596 298, EP-A-613 884, EP-A-613 885, DE 44 40 594, WO 94/01 997, WO 95/01 358, WO 95/20 572, EP-A-668 267, WO 95/26 954, WO 96/25395 and the not yet published German patent application by the applicant dated December 6, 1995 with the file number 19545467.7).

It is known that certain substituted Δ ³ -dihydrofuran-2-one derivatives have herbicidal properties (cf. DE-A-40 14 420). The synthesis of the tetronic acid derivatives used as starting compounds (such as, for example, 3- (2-methylphenyl) -4-hydroxy-5- (4-fluorophenyl) -Δ ³ -dihydrofuranone- (2)) is also described in DE- A-40 14 420. Similar structured compounds without an insecticidal and / or acaricidal activity are known from the publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985, (8) 1567-76. Furthermore, 3-aryl-Δ ³ -dihydrofuranone derivatives with herbicidal, acaricidal and insecticidal properties from EP-A-528 156, EP-A-0 647 637, WO 96/25395, WO 96/20196 and the above are not yet published patent application known. 3-Aryl-Δ ³ -di hydrothiophen-one derivatives are also known (WO 95/26 345, WO 96/25395 and the above-mentioned patent application which has not yet been disclosed).

The acaricidal and insecticidal activity and / or activity range and / or the Plant tolerance of these compounds, in particular to crop plants, however, is not always sufficient.  

New compounds of the formula (I)

found,
in which
V represents hydrogen, halogen, alkyl or alkoxy,
W represents hydrogen cyano, nitro, halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy, in each case optionally substituted phenyl, phenoxy, phenylthio, phenylalkoxy or phenylalkylthio,
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy, cyano, nitro, in each case optionally substituted phenyl, phenoxy, phenylthio, phenylalkyloxy or phenylalkylthio,
Y represents hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, cyano or nitro,
Z represents hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, hydroxy, cyano, nitro or in each case optionally substituted phenoxy, phenylthio, 5- or 6-membered hetaryloxy, 5- or 6-membered hetarylthio, phenylalkyloxy or phenylalkylthio, or
Y and Z together with the carbon atoms to which they are attached represent an optionally substituted cycle which is optionally interrupted by one or more heteroatoms, or
W and Z together with the carbon atoms to which they are attached represent an optionally substituted cycle which may be interrupted by one or more heteroatoms,
Het for one of the groups

stands,
wherein
G for hydrogen (a) or for one of the groups

stands,
wherein
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R ^{1 represents} in each case optionally substituted by halogen or cyano substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl or for in each case optionally substituted by halogen, alkyl or alkoxy cycloalkyl or heterocyclyl or for optionally substituted or unsubstituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
R ² represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, each optionally substituted by halogen or cyano, or represents optionally substituted cycloalkyl, phenyl or benzyl,
R ³ , R ⁴ and R ⁵ independently of one another each represent optionally substituted by halogen substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio or represent optionally substituted phenyl, benzyl, phenoxy or phenylthio,
R ⁶ and R ⁷ independently of one another represent hydrogen, each optionally substituted by halogen or cyano-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, each optionally substituted phenyl or benzyl, or together with the N atom to which they are attached are, if appropriate, form an oxygen or sulfur-containing and optionally substituted cycle.

The compounds of formula (I) can, depending on the nature of the sub substituents, as optical isomers or isomer mixtures, in different contexts are available, which may or may not be separated in the usual way can. Both the pure isomers and the isomer generic niche, the origin Position and use as well as means containing them are the subject of this  invention. For the sake of simplicity, however, Ver Compounds of formula (I) spoken, although both the pure compounds as optionally also mixtures with different proportions of isomeric compound are meant.

Including the meanings (1) to (3) of the Het group, the following main structures (I-1) to (I-3) result:

wherein
G, V, W, X, Y and Z have the meaning given above.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following main structures (I-1-a) to (I -1-g) when Het represents group (I),

wherein
E, L, M, V, W, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meanings given above.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following main structures (I-2-a) to (I -2-g) when Het represents group (2),

wherein
E, L, M, V, W, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meaning given above.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following main structures (I-3-a) to (I -3-g) when Het represents group (3),

wherein
E, L, M, V, W, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meanings given above.

Furthermore, it was found that the new compounds of the formula (I) can be obtained by the processes described below:

• (A) Compounds of the formula (I-1-a) are obtained
  in which
  V, W, X, Y and Z have the meanings given above,
  if
  Compounds of formula (II)
  in which
  V, W, X, Y and Z have the meanings given above,
  and
  R ^{8 represents} alkyl (preferably C ₁ -C ₆ alkyl),
  condensed intra-molecularly in the presence of a diluent and in the presence of a base.
• (B) It has also been found that compounds of the formula (I-2-a)
  in which
  V, W, X, Y and Z have the meanings given above,
  get when one
  Compounds of formula (III)
  in which
  V, W, X, Y, Z and R ^{8 have} the meanings given above,
  condensed intra-molecularly in the presence of a diluent and in the presence of a base.
• (C) It was also found that compounds of the formula (I-3-a)
  in which
  V, W, X, Y and Z have the meanings given above,
  get when one
  Compounds of formula (IV)
  in which
  V, W, X, Y, Z and R ^{8 have} the meanings given above and
  T represents hydrogen, halogen, alkyl (preferably C ₁ -C ₆ alkyl) or alkoxy (preferably C ₁ -C ₈ alkoxy),
  optionally cyclized intramolecularly in the presence of a diluent and in the presence of an acid.

It was also found

• (D) that the compounds of the formulas (I-1-b) to (I-3-b) shown above, in which R ¹ , V, W, X, Y and Z have the meanings given above, are obtained if compounds of the formulas (I-1-a) to (I-3-a) shown above, in which V, W, X, Y and Z have the meanings given above, in each case
  • α) with acid halides of the formula (V)
    in which
    R ^{1 has} the meaning given above and
    Hal stands for halogen (especially chlorine or bromine)
    or
  • β) with carboxylic anhydrides of the formula (VI) R ¹ -CO-O-CO-R ¹ (VI) in which
    R ^{1 has} the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
• (E) that the compounds of the formulas (I-1-c) to (I-3-c) shown above, in which R ² , V, W, M, X, Y and Z have the meanings given above and L represents oxygen, is obtained when compounds of the formulas (I-1-a) to (I-3-a) shown above, in which V, W, X, Y and Z have the meanings given above, in each case
  with chloroformate or chloroformate thioester of formula (VII) R ² -M-CO-Cl (VII) in which
  R ² and M have the meanings given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
• (F) that compounds of the formulas (I-1-c) to (I-3-c) shown above, in which R ² , V, W, M, X, Y and Z have the meanings given above and L for Sulfur is obtained if compounds of the formulas (I-1-a) to (I-3-a) shown above, in which V, W, X, Y and Z have the meanings given above, are obtained in each case
  with chloromothio formic acid esters or chlorodithio formic acid esters of the formula (VIII)
  in which
  M and R ^{2 have} the meanings given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
• (G) that compounds of the formulas (I-1-d) to (I-3-d) shown above, in which R ³ , V, W, X, Y and Z have the meanings given above, are obtained if Compounds of the formulas (I-1-a) to (I-3-a) shown above, in which V, W, X, Y and Z have the meanings given above, in each case
  with sulfonic acid chlorides of the formula (IX) R ³ -SO ₂ -Cl (IX) in which
  R ^{3 has} the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
• (H) that compounds of the formulas (I-1-e) to (I-3-e) shown above, in which L, R ⁴ , R ⁵ , V, W, X, Y and Z have the meanings given above , is obtained when compounds of the formulas (I-1-a) to (I-3-a) shown above, in which V, W, X, Y and Z have the meanings given above, in each case
  with phosphorus compounds of formula (X)
  in which
  L, R ⁴ and R ^{5 have} the meanings given above and
  Hal represents halogen (especially chlorine or bromine),
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
• (I) that compounds of the formulas (I-1-f) to (I-3-f) shown above, in which E, V, W, X, Y and Z have the meanings given above, are obtained when compounds of the formulas (I-1-a) to (I-3-a), in which V, W, X, Y and Z have the meanings given above, in each case
  with metal compounds or amines of the formulas (X) or (XI)
  in which
  Me for a mono- or divalent metal (preferably an alkali or alkaline earth metal such as lithium, sodium, potassium, magnesium or calcium),
  t for the number 1 or 2 and
  R ¹⁰ , R ¹¹ , R ¹² independently of one another represent hydrogen or alkyl (preferably C ₁ -C ₈ alkyl), optionally reacted in the presence of a diluent,
• (J) that compounds of the formulas (I-1-g) to (I-3-g) shown above, in which L, R ⁶ , R ⁷ , V, W, X, Y and Z have the meanings given above , is obtained when compounds of the formulas (I-1-a) to (I-3-a) shown above, in which V, W, X, Y and Z have the meanings given above, in each case
  • α) with isocyanates or isothiocyanates of the formula (XII) R ⁶ -N = C = L (XII)
    in which
    R ⁶ and L have the meanings given above,
    if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst or
  • β) with carbamic acid chlorides or thiocarbamic acid chlorides of the formula (XV)
    in which
    L, R ⁶ and R ^{7 have} the meanings given above,
    optionally in the presence of a diluent and, if appropriate, in the presence of an acid binder.

It has also been found that the new compounds of the formula (I) are very good Efficacy as a pesticide, preferably as an insecticide, Akari exhibit cides and herbicides and, moreover, often very well tolerated by plants, especially to crops.

The compounds according to the invention are generally defined by the formula (I). Preferred substituents or ranges of those mentioned in the above and below The radicals listed in formulas are explained below:

V preferably represents hydrogen, halogen, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy.

W preferably represents hydrogen nitro, cyano, halogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy, C ₁ -C ₄ haloalkyl , C ₁ -C ₄ haloalkoxy or in each case optionally substituted by halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy, nitro or cyano Phenyl, phenoxy, phenylthio, phenyl-C ₁ -C ₄ -alkoxy or phenyl-C ₁ -C ₄ -alkylthio.

X preferably represents halogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ -haloalkoxy, cyano, nitro or phenyl optionally substituted by halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -haloalkoxy, nitro or cyano , Phenoxy, phenylthio, phenyl-C ₁ -C ₄ -alkoxy or phenyl-C ₁ -C ₄ -alkylthio.

Y is preferably hydrogen, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ - C ₄ haloalkyl, C ₁ -C ₄ -haloalkoxy, cyano or nitro.

Z preferably represents hydrogen halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ - C ₄ -haloalkyl, C ₁ -C ₄ -haloalkoxy, hydroxy, cyano, nitro or in each case optionally by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ halo alkyl, C ₁ -C ₄ haloalkoxy, nitro or cyano substituted phenoxy, phenylthio, thiazolyloxy, pyridinyloxy, pyrimidyloxy, pyrazolyloxy, phenyl - C ₁ -C ₄ alkyloxy or phenyl-C ₁ -C alkylthio or

Y and Z are preferably together with the carbon atoms to which they are attached, represent optionally halogen-, C ₁ -C ₆ alkyl, C ₁ - C ₆ alkoxy or C ₁ -C ₄ -halogenoalkyl-substituted C ₃ -C ₅ -alkanediyl or C ₃ - C ₅ -alkenediyl, in which optionally one to three members can be replaced independently by oxygen, sulfur, nitrogen or a carbonyl group, or

W and Z together with the carbon atoms to which they are attached represent
each optionally substituted by halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy or C ₁ - C ₄ -haloalkyl-substituted C ₃ -C ₅ -alkanediyl or C ₃ -C ₅ -alkenediyl, in which one to three Limbs can be replaced independently of one another by oxygen, sulfur, nitrogen or a carbonyl group.

Het preferably represents one of the groups

stands,

G preferably represents hydrogen (a) or one of the groups

in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M stands for oxygen or sulfur.

R ¹ preferably represents in each case optionally substituted by halogen or cyano substituted C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₁ -C ₈ alkoxy-C ₁ -C ₈ alkyl, C ₁ -C ₈ -Alkylthio-C ₁ -C ₈ alkyl or poly-C ₁ -C ₈ alkoxy-C ₁ -C ₈ alkyl or for optionally substituted by halogen, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy C ₃ -C ₈ cycloalkyl, in which one or two methylene groups which are not directly adjacent are optionally replaced by oxygen and / or sulfur,
for optionally by halogen, cyano, nitro, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio or C ₁ -C ₆ alkylsulfonyl substituted phenyl,
is optionally substituted by halogen, nitro, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ haloalkoxy-C ₁ -C ₆ alkyl ,
for 5- or 6-membered hetaryl optionally substituted by halogen or C ₁ -C ₆ -alkyl and having one or two heteroatoms from the series consisting of oxygen, sulfur and nitrogen
is optionally substituted by halogen or C ₁ -C ₆ -alkyl-substituted phenoxy-C ₁ -C ₆ alkyl, or
for 5- or 6-membered hetaryloxy-C ₁ -C ₆ alkyl optionally substituted by halogen, amino or C ₁ -C ₆ alkyl and having one or two heteroatoms from the series consisting of oxygen, sulfur and nitrogen.

R ² preferably represents in each case optionally substituted by halogen or cyano-substituted C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₁ -C ₃ alkoxy-C ₂ -C ₈ alkyl or poly-C ₁ -C _8- alkoxy-C ₂ -C ₈ -alkyl,
for C ₃ -C ₈ cycloalkyl optionally substituted by halogen, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy or
for phenyl or benzyl optionally substituted by halogen, cyano, nitro, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ haloalkoxy.

R ³ preferably represents optionally halogen-substituted C ₁ -C ₈ -alkyl or in each case optionally substituted by halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ - C ₄ haloalkyl, C ₁ -C ₄ -haloalkoxy, cyano or nitro substituted phenyl or benzyl.

R ⁴ and R ⁵ independently of one another preferably each represent C ₁ -C ₈ -alkyl optionally substituted by halogen, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -alkylamino, di- (C ₁ -C ₈ -alkyl) amino, C ₁ -C ₈ alkylthio or C ₃ -C ₈ alkenylthio or for each optionally halogen, nitro, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - haloalkoxy, C ₁ -C ₄ - Alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl substituted phenyl, phenoxy or phenylthio.

R ⁶ and R ⁷ independently of one another preferably represent hydrogen, represents in each case optionally substituted by halogen or cyano C ₁ -C ₈ alkyl, C ₃ -C ₈ - cycloalkyl, C ₁ -C ₈ alkoxy, C ₃ -C ₈ alkenyl or C ₁ -C ₈ alkoxy-C ₂ -C ₈ alkyl, each for phenyl or benzyl optionally substituted by halogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ haloalkyl or C ₁ -C ₈ alkoxy or together for a C ₃ -C ₆ -alkylene radical which is optionally substituted by C ₁ -C ₆ -alkyl and in which a methylene group is optionally replaced by oxygen or sulfur.

V particularly preferably represents hydrogen fluorine, chlorine, bromine, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy.

W particularly preferably represents hydrogen nitro, cyano, fluorine, chlorine, bromine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkoxy or in each case if appropriate phenyl, phenoxy, benzyl or substituted by fluorine, chlorine, bromine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkoxy, nitro or cyano Benzyloxy.

X particularly preferably represents fluorine, chlorine, bromine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkoxy, cyano, nitro or, if appropriate, in each case by fluorine, chlorine, bromine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkoxy, nitro or cyano substituted phenyl, phenoxy, benzyl or benzyloxy .

Y particularly preferably represents hydrogen fluorine, chlorine, bromine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkoxy, cyano or nitro.

Z particularly preferably represents hydrogen fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -haloalkyl, C ₁ -C ₂ -haloalkoxy, hydroxy, cyano, nitro or each optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkoxy, nitro or cyano, or phenoxy or benzyloxy, or

Y and Z are particularly preferably together with the carbon atoms to which they are attached, represent optionally fluorine-, chlorine, bromine, C ₁ - C ₄ alkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₂ -haloalkyl substituted C ₃ -C ₄ -alkanediyl or C ₃ -C ₄ -alkenediyl, in which one or two not directly adjacent members can optionally be replaced independently of one another by oxygen, sulfur or nitrogen, or

W and Z are particularly preferably together with the carbon atoms to which they are attached, represent optionally fluorine-, chlorine, bromine, C ₁ - C ₄ alkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₂ -haloalkyl substituted C ₃ -C ₄ -alkanediyl or C ₃ -C ₄ -alkenediyl, in which one or two not directly adjacent members can be replaced independently of one another by oxygen, sulfur or nitrogen.

Het is particularly preferably one of the groups

stands

G is particularly preferred for hydrogen (a) or for one of the groups

in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M stands for oxygen or sulfur.

R ¹ particularly preferably represents C ₁ -C ₁₆ -alkyl, C ₂ -C ₁₆ -alkenyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₁ -C _6, each optionally substituted by fluorine or chlorine -Alkylthio-C ₁ -C ₆ -alkyl or poly-C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl or for optionally by fluorine, chlorine, C ₁ -C ₅ -alkyl or C ₁ -C ₅ - Alkoxy-substituted C ₃ -C ₇ cycloalkyl, in which one or two not directly adjacent methylene groups are optionally replaced by oxygen and / or sulfur,
is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ alkyl, C ₁ - C ₄ alkoxy, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ haloalkoxy, C ₁ -C ₄ -Alkylthio or C ₁ -C ₄ -alkylsulfonyl-substituted phenyl,
for phenyl-C ₁ -C ₄ -alkyl which is optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -haloalkyl or C ₁ -C ₃ -haloalkoxy ,
for each pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl,
for optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₄ alkyl phenoxy-C ₁ -C ₅ alkyl or
for in each case optionally substituted by fluorine, chlorine, bromine, amino or C ₁ -C ₄ alkyl substituted pyridyloxy-C ₁ -C ₅ alkyl, pyrimidyloxy-C ₁ -C ₅ alkyl or thi azolyloxy-C ₁ -C ₅ alkyl .

R ² particularly preferably represents in each case optionally substituted by fluorine or chlorine, C ₁ -C ₁₆ -alkyl, C ₂ -C ₁₆ -alkenyl, C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl or poly-C ₁ - C ₆ alkoxy-C ₂ -C ₆ alkyl,
for C ₃ -C ₇ cycloalkyl optionally substituted by fluorine, chlorine, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy or
for phenyl or benzyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₃ haloalkyl or C ₁ -C ₃ haloalkoxy .

R ³ particularly preferably represents C ₁ -C ₆ -alkyl optionally substituted by fluorine or chlorine or in each case optionally by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -Halogenalkoxy, C ₁ -C ₂ -halogen alkyl, cyano or nitro substituted phenyl or benzyl.

R ⁴ and R ⁵ independently of one another particularly preferably each represent C ₁ -C ₆ -alkyl which is optionally substituted by fluorine or chlorine, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylamino, di- (C ₁ -C ₆ -alkyl) amino, C ₁ -C ₆ -alkylthio or C ₃ -C ₄ -alkenylthio or for each optionally by fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -haloalkoxy , C ₁ -C ₃ alkylthio, C ₁ - C ₃ haloalkylthio, C ₁ -C ₃ alkyl or C ₁ -C ₃ haloalkyl substituted phenyl, phenoxy or phenylthio.

R ⁶ and R ⁷ , independently of one another, particularly preferably represent hydrogen, in each case optionally substituted by fluorine or chlorine, C ₁ -C ₆ -alkyl, C ₃ - C ₆ -cycloalkyl, C ₁ -C ₆ -alkoxy, C ₃ -C ₆ - Alkenyl or C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkyl, for each optionally by fluorine, chlorine, bromine, C ₁ -C ₅ halo alkyl, C ₁ -C ₅ alkyl or C ₁ -C ₅ - alkoxy-substituted phenyl or benzyl, or together represent an optionally C ₁ -C ₄ alkyl-substituted C ₃ - C ₆ -alkylene radical in which optionally one methylene group is replaced by oxygen or sulfur.

V very particularly preferably represents hydrogen fluorine, chlorine, bromine, methyl, Ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, propoxy or iso- Propoxy.  

W very particularly preferably represents hydrogen nitro, cyano, fluorine, chlorine, Bromine, methyl, ethyl, propyl, butyl, iso-propyl, iso-butyl, tert-butyl, Methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl, difluoromethoxy, Trifluoromethoxy, phenyl or benzyloxy.

X very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, propyl, Butyl, iso-butyl, iso-propyl, tert-butyl, methoxy, ethoxy, propoxy, iso- Propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano, nitro, Phenyl or benzyloxy.

Y very particularly preferably represents hydrogen fluorine, chlorine, bromine, methyl, Ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, methoxy, ethoxy, Propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, Cyano or nitro.

Z very particularly preferably represents hydrogen fluorine, chlorine, bromine, methyl, Ethyl, propyl, butyl, iso-butyl, iso-propyl, tert-butyl, methoxy, ethoxy, Propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, Cyano or nitro, or

Y and Z very particularly preferably, together with the carbon atoms to which they are attached, represent C ₃ optionally substituted by fluorine, chlorine, methyl, ethyl, propyl, iso-propyl, methoxy, ethoxy, propoxy, iso-propoxy or trifluoromethyl -C ₄ -alkanediyl, in which, if appropriate, two not directly adjacent members are replaced by oxygen or

W and Z very particularly preferably, together with the carbon atoms to which they are attached, represent C ₃ optionally substituted by fluorine, chlorine, methyl, ethyl, propyl, iso-propyl, methoxy, ethoxy, propoxy, iso-propoxy or trifluoromethyl -C ₄ -alkanediyl, in which two optionally not directly adjacent members are replaced by oxygen.

Het very particularly preferably stands for one of the groups

stands,

G very particularly preferably represents hydrogen (a) or one of the groups

in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M stands for oxygen or sulfur.

R ¹ very particularly preferably represents in each case optionally substituted by fluorine or chlorine, C ₁ -C ₁₄ alkyl, C ₂ -C ₁₄ alkenyl, C ₁ -C ₄ -alkoxy-C ₁ -C ₆ - alkyl, C ₁ -C _4- alkylthio-C ₁ -C ₆ -alkyl, poly-C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl or for optionally by fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n -Butyl, i-butyl, tert-butyl, methoxy, ethoxy, n-propoxy or iso-propoxy substituted C ₃ -C ₆ cycloalkyl, in which one or two non-directly adjacent methylene groups are optionally replaced by oxygen and / or sulfur ,
for phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl,
for benzyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
for furanyl, thienyl or pyridyl optionally substituted by fluorine, chlorine, bromine, methyl or ethyl,
for optionally substituted by fluorine, chlorine, methyl or ethyl phenoxy-C ₁ -C ₄ alkyl or
for in each case optionally substituted by fluorine, chlorine, amino, methyl or ethyl pyridyloxy-C ₁ -C ₄ -alkyl, pyrimidyloxy-C ₁ -C ₄ -alkyl or thiazolyloxy-C ₁ -C ₄ -alkyl.

R ² very particularly preferably represents C ₁ -C ₁₄ -alkyl, C ₂ -C ₁₄ -alkenyl, C ₁ -C ₄ -alkoxy-C ₂ -C ₆ -alkyl or poly-C _1, each optionally substituted by fluorine or chlorine -C ₄ alkoxy-C ₂ -C ₆ alkyl,
for C ₃ -C ₆ cycloalkyl optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl or methoxy,
or for phenyl or benzyl optionally substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy.

R ³ very particularly preferably represents methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, which is optionally substituted by fluorine or chlorine, or in each case optionally by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert .-Butyl, methoxy, ethoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro substituted phenyl or benzyl.

R ⁴ and R ⁵ independently of one another very particularly preferably each represent C ₁ -C ₄ -alkyl which is optionally substituted by fluorine or chlorine, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, di- (C ₁ -C _{4 ) 4-} alkyl) amino or C ₁ -C ₄ -alkylthio or for phenyl, phenoxy or phenylthio which are each optionally substituted by fluorine, chlorine, bromine, nitro, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy.

R ⁶ and R ⁷ independently of one another very particularly preferably represent hydrogen for C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₃ -C _4, each optionally substituted by fluorine or chlorine -Alkenyl or C ₁ -C ₄ -alkoxy-C ₂ - C ₄ -alkyl, each for phenyl or benzyl optionally substituted by fluorine, chlorine, bromine, methyl, methoxy or trifluoromethyl, or together for one optionally substituted by methyl or ethyl C ₅ -C ₆ alkylene radical in which a methylene group is optionally replaced by oxygen or sulfur.

The general or priority ranges listed above nitions or explanations can be among each other, that is, between the respective Areas and preferred areas can be combined as desired. They apply to the End products as well as for the preliminary and intermediate products accordingly.  

According to the invention, preference is given to the compounds of the formula (I) in which one Combination of the meanings listed above as preferred (preferred) is present.

According to the invention, particular preference is given to the compounds of the formula (I), in which are a combination of those listed as particularly preferred above Meanings exist.

According to the invention, very particular preference is given to the compounds of the formula (I) in which a combination of the above is particularly preferred meanings.

Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can also in connection with heteroatoms such as e.g. B. in alkoxy, where possible, each straight chain or branched.

Optionally substituted radicals can be mono- or polysubstituted, in the case of multiple substitutions, the substituents are the same or different can.

In particular, except for the compounds mentioned in the preparation examples the following compounds of formula (I-1-a) called:  

Table 1

In particular, except for the compounds mentioned in the preparation examples the following compounds of formula (I-2-a) called.

Table 2

in which
V, W, X, Y and Z have the meanings given in Table 1.

In particular, except for the compounds mentioned in the preparation examples the following compounds of formula (I-3-a) called.

Table 3

in which
V, W, X, Y and Z have the meanings given in Table 1.

If N - [(4-chloro-2,6-dimethyl) phenylacetyl] -3-amino-3-carboxyethyl-tetrahydropyran is used as starting material in process (A), the course of the process according to the invention can be represented by the following reaction scheme:

If O - [(2-chloro-6-methyl) -phenylacetyl] -3-hydroxy-3-carboxyethyl-tetrahydropyran is used in process (B), the course of the process according to the invention can be represented by the following reaction scheme:

If 2 - [(2-chloro-4,6-dimethyl) phenyl] -4- (4-meth oxy) -benzylmercapto-4,4-methyleneoxypropyl-3-oxo-valeric acid ethyl ester is used according to process (c), the course of the process according to the invention can be represented by the following reaction scheme:

If 3 - [(2-chloro-4-methyl) -phenyl] -5,5-methylene oxypropyl-pyrrolidin-2,4-dione and pivaloyl chloride are used as starting materials in process (Dα), the course of the process according to the invention can be followed by the following reaction scheme can be given:

If, in accordance with process (D) (variant β), 3 - [(2,4-dichloro) phenyl] -4-hydroxy-5,5-methyleneoxypropyl-Δ ³ -dihydrofuran-2-one and acetic anhydride are used as starting compounds, the course of the process according to the invention can be reproduced by following the reaction scheme:

If 8 - [(2,4-dichloro) phenyl] -5,5-methyleneoxy propyl-pyrrolidine-2,4-dione and ethyl chloroformate are used as starting compounds in process (E), the course of the process according to the invention can be determined by the following Reaction scheme are reproduced:

If, according to process (F), 3 - [(2, 6-dibromo-4-methyl) -phenyl] -4-hydroxy-5,5-methyleneoxypropyl-Δ ³ -dihydrofuran-2-one and methyl chloroformate are used as starting products, so the course of the reaction can be represented as follows:

If 2 - [(2,4,6-trimethyl) phenyl] -5,5-methylene oxypropyl-pyrrolidine-2,4-dione and methanesulfonic acid chloride are used as starting products in process (G), the course of the reaction can be represented by the following reaction scheme will:

According to process (H) 2 - [(4-bromo-2-chloro-6-methyl) -phenyl] -4-hydroxy-5,5-methyleneoxypropyl-Δ ³ -dihydrofuran-2-one and methanthophosphonic acid are used chloride (2,2,2-trifluoroethyl ester) as starting products, the course of the reaction can be represented by the following reaction scheme:

If 3 - [(2,4-dichloro) -6-methylphenyl] -5,5-methylene lenoxypropyl-pyrrolidine-2,4-dione and NaOH are used as components according to process (I), the course of the process according to the invention can be determined by the following reaction scheme can be reproduced:

According to process (J) (variant α) 3 - [(2-chloro-4-bromo-5-methyl) - phenyl] -4-hydroxy-5,5-methyleneoxypropyl-Δ ³ -dihydro-furan-2- on and ethyl isocyanate as starting products, the course of the reaction can be represented by the following reaction scheme:

If, according to process (J) (variant β), 3 - [(2-chloro-4,6-dimethyl) phenyl] - 5,5-methyleneoxypropyl-pyrrolidine-2,4-dione and dimethyl carbamic acid chloride are used as starting products, the The course of the reaction can be reproduced using the following scheme:

The compounds of the formula (II) required as starting materials in process (A) according to the invention

in which
V, W, X, Y, Z and R ^{8 have} the meanings given above,
are new.

The acylamino acid esters of the formula (II) are obtained, for example, if amino acid derivatives of the formula (XV)

in which
R ^{8 has} the meaning given above,
with substituted phenylacetic acid halides of the formula (XVI)

in which
V, W, X, Y and Z have the meanings given above and
Hal represents chlorine or bromine,
acylated (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem. 6, 341-5, 1968)
or if you have acylamino acids of the formula (XVII)

in which
V, W, X, Y and Z have the meanings given above,

esterified (Chem. Ind. (London) 1568 (1968)).

The compounds of formula (XVII)

in which
V, W, X, Y and Z have the meanings given above,
are new.

The compounds of the formula (XVII) are obtained, for example, if 3-amino-tetrahydropyran-3-carboxylic acid of the formula (XVIII)

with substituted phenylacetic acid halides of the formula (XVI)

in which
V, W, X, Y and Z have the meanings given above,
Hal represents chlorine or bromine,
acylated according to Schotten-Baumann (Organikum, VEB German Publishing House of Sciences, Berlin 1977, p. 505).

The compounds of formula (XVI) are partly new and can be after known processes (see e.g. the as yet unpublished German patent applications of the applicant dated January 31, 1996 with the file number 19603332.2, from January 25th, 1996 with the file number 19602524.9 and from April 2nd, 1996 with the Case number 19613171.5).

The compounds of the formula (XVI) are obtained, for example, by substituting substituted phenylacetic acids of the formula (XIX)

in which
V, W, X, Y and Z have the meaning given above,
with halogenating agents (e.g. thionyl chloride, tbionyl bromide, oxalyl chloride, phos gene, phosphorus trichloride, phosphorus tribromide or phosphorus pentachloride) optionally in the presence of a diluent (e.g. optionally chlorinated aliphatic or aromatic hydrocarbons such as toluene or methylene chloride) at temperatures of -20 ° C to 150 ° C, preferably from -10 ° C to 100 ° C, implemented.

Some of the compounds of the formula (XIX) are new; they can be prepared by processes known from the literature (Organikum 15th edition, p. 533, VEB Deutscher Verlag der Wissenschaften, Berlin 1977, cf. e.g. the as yet unpublished German patent applications the applicant from January 31, 1996 with the file number 19603332.2, from January 25, 1996 with the file number 19602524.9 and from April 2, 1996 with the file number 19613171.5). The compounds of the formula (XIX) are obtained, for example, by substituting substituted phenylacetic acid esters of the formula (XX)

in which
V, W, X, Y, Z and R ^{8 have} the meaning given above,
in the presence of an acid (e.g. an inorganic acid such as hydrochloric acid) or a base (e.g. an alkali hydroxide such as sodium or potassium hydroxide) and optionally a diluent (e.g. an aqueous alcohol such as methanol or ethanol) Temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 100 ° C, hydrolyzed.

Some of the compounds of the formula (XX) are new, and in principle they can be used produce known methods.

The compounds of the formula (XX) are obtained, for example, by substituting 1,1,1-trichloro-2-phenylethanes of the formula (XXI)

in which
V, W, X, Y and Z have the meaning given above,
first with alcoholates (e.g. alkali metal alcoholates such as sodium methylate or sodium ethylate) in the presence of a diluent (e.g. alcohol derived from the alcoholate) at temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C , and then with an acid (preferably an inorganic acid such as sulfuric acid) at temperatures between -20 ° C and 150 ° C, preferably 0 ° C and 100 ° C, (see. DE 33 14 249).

Some of the compounds of the formula (XXI) are new; produce known methods.

The compounds of the formula (XXI) are obtained, for example, if anilines of the formula (XXII)

in which
V, W, X, Y and Z have the meaning given above,
in the presence of an alkyl nitrite of the formula (XXIII)

R ¹³ -ONO (XXIII)

in which
R ^{13 represents} alkyl, preferably C ₁ -C ₆ alkyl,
in the presence of copper (II) chloride and optionally in the presence of a diluent (e.g. an aliphatic nitrile such as acetonitrile) at a temperature of from -20 ° C to 80 ° C, preferably 0 ° C to 60 ° C Vinylidene chloride (CH ₂ = CCl ₂ ) is implemented.

The compounds of formula (XXII) are partially known compounds. she can, however, be represented by methods established in the literature, for example by reducing the corresponding nitro compounds or halogenating the Anilines or acetanilides and subsequent cleavage.

The compounds of formula (XXIII) are known organic compounds Chemistry. Copper (II) chloride and vinylidene chloride have long been known and commercially available.

The compounds of formula (XV) and (XVIII) are new and can be after known methods (see e.g. Compagnon, Ann. Chim. (Paris) [14] 5, p. 11-22, 23-27 (1970), L. Munday, J. Chem. Soc. 4372 (1961); J.T. Eward, C. Jitrangeri, Can. J. Chem. 53, 3339 (1975).

The starting materials of the formula (II) used in process (A) above can also be

in which
V, W, X, Y, Z and R ^{8 have} the meanings given above,
produce if 3-amino-tetrahydropyran-3-carbonitrile of the formula (XXIV)

with substituted phenylacetic acid halides of the formula (XVI)

in which
V, W, X, Y, Z and Hal have the meanings given above,
to compounds of the formula (XXV)

in which
V, W, X, Y and Z have the meanings given above,
implements
and then subjecting it to acidic alcoholysis.

The compounds of formula (XXV) are also new. The compound of the formula (XXIV) is also new.

The compounds of the formula (III) required as starting materials in process (B) according to the invention

in which
V, W, X, Y, Z and R ^{8 have} the meanings given above,
are new.

They can be produced in a simple manner using methods which are known in principle.

The compounds of the formula (III) are obtained, for example, if 3-hydroxy-tetrahydropyran-3-carboxylic acid esters of the formula (XXVI)

in which
R ^{8 has} the meaning given above,
with substituted phenylacetic acid halides of the formula (XVI)

in which
V, W, X, Y, Z and Hal have the meanings given above,
acylated (Chem. Reviews 52, 237-416 (1953)).

The 3-hydroxy-tetrahydropyran-3-carboxylic acid esters of the formula (XXVI) are new. They are obtained, for example, by using 3-hydroxy-tetrahydropyran-3-carboxylic acid nitrile of the formula (XXVI-a) in the presence of acids, e.g. B. alcoholized according to Pinner (see manufacturing example). The cyanohydrin is obtained, for example, by reaction of tetrahydropyran-3-one with hydrocyanic acid.

The compounds of the formula (IV) required as starting materials in process (C) above

in which
T, V, W, X, Y, Z and R ^{8 have} the meanings given above,
are new.

They can be produced using methods that are known in principle.

The compounds of the formula (IV) are obtained, for example, if substituted phenylacetic acid esters of the formula (XX)

in which
V, W, X, Y, R ⁸ and Z have the meanings given above,

with 2-benzylthio-carboxylic acid halides of the formula (XXVII)

in which
T has the meaning given above and
Hal represents halogen (especially chlorine or bromine),
acylated in the presence of strong bases (see, for example, BMS Chambers, EJ Thomas, DJ Williams, J. Chem. Soc. Chem. Commun., (1987), 1228).

The benzylthio-carboxylic acid halides of the formula (XXVII) are new. You leave are produced by known methods (J. Antibiotics (1983), 26, 1589).

The processes (D), (E), (F), (G), (H), (I) and (J) acid halides of the formula required as starting materials (V), carboxylic anhydrides of the formula (VI), chloroformate or chlorine formic acid thioesters of the formula (VII), chloromothio formic acid esters or Chlorodithio formic acid ester of the formula (VIII), sulfonic acid chlorides of the formula (IX), phosphorus compounds of formula (X) and metal hydroxides, metal alkoxides or amines of the formula (XI) and (XII) and isocyanates of the formula (XIII) and Carbamic acid chlorides of the formula (XIV) are generally known compounds organic or inorganic chemistry.

The compounds of formulas (XVI), (XIX), (XX), (XXI) and (XXII) are known and / or from the patent applications cited at the outset can be produced using the methods specified there (see also the  Applicant's unpublished German patent applications dated December 12, 1995 with the file number 19545467.7, dated January 25, 1996 with the file number 19602524.9, dated January 31, 1996 with the file number 19603332.2 and dated 04/02/1996 with the file number 19613171.5).

Process (A) is characterized in that compounds of the formula (II) in which V, W, X, Y, Z and R ^{8 have} the meanings given above, in the presence of a diluent and in the presence of a base of an intramolecular one Subject to condensation.

All of them can be used as diluents in process (A) according to the invention organic solvents inert to the reactants will. Hydrocarbons such as toluene and Xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, also polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone, and alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol and tert.- Butanol.

All conventional proton acceptors can be used as the base (deprotonating agent) when carrying out process (A) according to the invention. Before preferably usable are alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which in the presence of phase transfer catalysts such. B. triethylbenzylammonium chloride, tetra butylammonium bromide, Adogen 464 (= methyltrialkyl (C ₈ -C ₁₀ ) ammonium chloride) or TDA 1 (= tris (methoxyethoxyethyl) amine) can be used. Alkali metals such as sodium or potassium can also be used. Furthermore, alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcoholates, such as sodium methylate, sodium ethylate and potassium tert-butoxide, can be used.

The reaction temperature can be carried out when carrying out the Ver driving (A) can be varied within a wide range. In general one works at temperatures between -75 ° C and 200 ° C, preferably between -50 ° C and 150 ° C.

Process (A) according to the invention is generally carried out under atmospheric pressure carried out.

When carrying out process (A) according to the invention, the reak is set tion component of formula (II) and the deprotonating base in general in equimolar to about double equimolar amounts. However, it is also possible one or the other component in a larger excess (up to 3 moles) use.

The process (B) is characterized in that compounds of the formula (III) in which V, W, X, Y, Z and R ^{8 have} the meanings given above are condensed intramolecularly in the presence of a diluent and in the presence of a base .

All can be used as diluents in process (B) according to the invention organic solvents which are inert to the reactants the. Hydrocarbons such as toluene and xylene are preferably usable, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and Diglycol dimethyl ether, also polar solvents, such as dimethyl sulfoxide, Sulfolane, dimethylformamide and N-methyl-pyrrolidone. Alko get like methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol and tert-butanol can be used.  

All conventional proton acceptors can be used as the base (deprotonating agent) when carrying out process (B) according to the invention. Alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which can also be used in the presence of phase transfer catalysts such as e.g. B. triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 (= methyltrialkyl (C ₈ -C ₁₀ ) ammonium chloride) or TDA 1 (= tris (methoxyethoxyethyl) amine) can be used. Alkali metals such as sodium or potassium can also be used. Furthermore, alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcohols, such as sodium methylate, sodium ethylate and potassium tert-butoxide, can also be used.

The reaction temperature can be carried out when carrying out the Ver driving (B) can be varied within a wide range. In general one works at temperatures between -75 ° C and 200 ° C, preferably between -50 ° C and 150 ° C.

Process (B) according to the invention is generally carried out under atmospheric pressure carried out.

When carrying out process (B) according to the invention, the reak is set tion components of formula (III) and the deprotonating bases in general in approximately equimolar amounts. However, it is also possible to use one or the other To use component in a larger excess (up to 3 moles).

Process (C) is characterized in that compounds of the formula (IV) in which T, V, W, X, Y, Z and R ^{8 have} the meaning given above, in the presence of an acid and, if appropriate, in the presence of a diluent cyclized intramolecularly.

All of them can be used as diluents in process (C) according to the invention organic solvents which are inert to the reactants the. Hydrocarbons such as toluene and xylene are preferably usable, halogenated hydrocarbons such as dichloromethane, chloroform, ethylene chloride, chlorobenzene, dichlorobenzene, and also polar solvents, such as dime thylsulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone. Farther can alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, iso butanol, tert-butanol can be used.

If necessary, the acid used can also serve as a diluent.

As acid, all customary anor ganic and organic acids are used, such as. B. Halogen water Substance acids, sulfuric acid, alkyl, aryl and haloalkyl sulfonic acids, in particular halogenated alkyl carboxylic acids such. B. Trifluoroacetic acid used.

The reaction temperature can be carried out when carrying out the Ver driving (C) can be varied within a wide range. In general one works at temperatures between 0 ° C and 250 ° C, preferably between 50 ° C and 150 ° C.

Process (C) according to the invention is generally carried out under normal pressure carried out.

When carrying out process (C) according to the invention, the Reaction components of the formulas (IV) and the acid z. B. in equimolar men  a. However, it is optionally also possible to catalyze the acid Use quantities.

Process (D _α ) is characterized in that compounds of the formulas (I-1-a) to (I-3-a) are each reacted with carboxylic acid halides of the formula (V), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder .

All solvents which are inert towards the acid halides can be used as diluents in the process (D _α ) according to the invention. Preference can be used as hydrocarbons, such as gasoline, benzene, toluene, xylene and tetralin, also halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, also ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydro furan Dioxane, moreover carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as dimethylformamide, dimethyl sulfoxide and sulfolane. If the hydrolysis stability of the acid halide permits, the reaction can also be carried out in the presence of water.

Suitable acid binders for the reaction according to process (D _α ) according to the invention are all customary acid acceptors. Tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclonones (DBN), Hunig base and N, N-dimethylaniline, and also alkaline earth metal oxides, such as magnesium and calcium oxide, are also preferably used Alkali and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.

The reaction temperature can be varied within a substantial range in the process (D _α ) according to the invention. In general, temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.

When carrying out the process (D _α ) according to the invention, the starting materials of the formulas (I-1-a) to (I-3-a) and the carboxylic acid halide of the formula (V) are generally in each case used in approximately equivalent amounts. However, it is also possible to use the carboxylic acid halide in a larger excess (up to 5 mol). The processing takes place according to usual methods.

The process (Dβ) is characterized in that compounds of Formulas (I-1-a) to (I-3-a) each with carboxylic anhydrides of the formula (VI) optionally in the presence of a diluent and optionally in In the presence of an acid binder.

In the process according to the invention, (Dβ) can be used as diluent preferably those diluents are used that are also used in the Ver Use of acid halides are preferred. Furthermore can also be used in excess carboxylic anhydride at the same time as Ver act as a fertilizer.

Acid binders which may be added in process (Dβ) preferably those acid binders in question that are also in use of acid halides are preferred.

The reaction temperature can be internal in the process (Dβ) according to the invention can be varied within a larger range. Generally one works at Temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.  

When carrying out the method (Dβ) according to the invention Starting materials of the formulas (I-1-a) to (I-3-a) and the carboxylic acid hydride Formula (VI) is generally used in approximately equivalent amounts. However, it is also possible to use a larger excess of the carboxylic anhydride shot (up to 5 moles) to use. The processing takes place according to the usual method the.

The general procedure is to use diluents and in excess existing carboxylic acid anhydride and the resulting carboxylic acid Distillation or by washing with an organic solvent or with Water removed.

The process (E) is characterized in that compounds of the For meln (I-1-a) to (I-3-a) each with chloroformates or chlor ants acid thiol esters of formula (VII) optionally in the presence of a dilution by means of and optionally in the presence of an acid binder.

All of them come as acid binders in process (E) according to the invention usual acid acceptors into consideration. Tertiary are preferably used Amines such as triethylamine, pyridine, DABCO, DBU, DBN, Hunig base and N, N- Dimethyl-aniline, also alkaline earth metal oxides, such as magnesium and calcium oxide, also alkali and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate as well as alkali hydroxides such as sodium hydroxide and Potassium hydroxide.

All can be used as diluents in process (E) according to the invention inert to the chloroformates or chloroformates Solvents are used. Hydrocarbons are preferably usable, such as gasoline, benzene, toluene, xylene and tetralin, and also halogenated hydrocarbon substances such as methylene chloride, chloroform, carbon tetrachloride, chlorine  benzene and o-dichlorobenzene, also ketones, such as acetone and methyl isopropyl ketone, furthermore ethers such as diethyl ether, tetrahydrofuran and dioxane, above carboxylic acid esters such as ethyl acetate, and also nitriles such as acetonitrile and also strongly polar solvents, such as dimethylformamide, dimethyl sulfoxide and Sulfolan.

The reaction temperature can be carried out when carrying out the Ver driving (E) can be varied within a wide range. The reaction tem temperature is generally between -20 ° C and + 100 ° C, preferably between 0 ° C and 50 ° C.

Process (E) according to the invention is generally carried out under atmospheric pressure carried out.

When performing the method (E) according to the invention, the off Starting materials of the formulas (I-1-a) to (I-3-a) and the corresponding chlor ants Acid esters or chloroformic acid thiol esters of the formula (VII) in general each because used in approximately equivalent amounts. However, it is also possible one or the other component in a large excess (up to 2 mol) to use. The processing takes place according to usual methods. In general the procedure is to remove precipitated salts and the remaining reak concentrated by pulling off the diluent.

Process (F) according to the invention is characterized in that Compounds of the formulas (I-1-a) to (I-3-a) each with compounds of the formula (VIII) in the presence of a diluent and optionally in the presence an acid binder.

In the production process (F), the per mole of starting compound Formulas (I-1-a) to (I-3-a) approx. 1 mol of chloromothio formic acid ester or chlorine  dithio formic acid ester of formula (VIII) at 0 to 120 ° C, preferably at 20 up to 60 ° C.

All inert polar come as optionally added diluents organic solvents in question, such as ethers, amides, sulfones, sulfoxides, but also halogen alkanes.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, Ethyl acetate or methylene chloride used.

Is made in a preferred embodiment by adding strong Depro toning agents such as B. sodium hydride or potassium tert-butylate the enolate salt of the compounds (I-1-a) to (I-3-a), can be based on the further addition of acid be dispensed with.

All conventional proton acceptors can be used as bases in process (F) will. Alkali metal hydrides, alkali metal alcohol are preferably usable latex, alkali or alkaline earth metal carbonates or hydrogen carbonates or stick fabric bases. Examples include sodium hydride, sodium methoxide, Sodium hydroxide, calcium hydroxide, potassium carbonate, sodium hydrogen carbonate, Triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline, diazabicyclo octane (DABCO), diazabicyclonones (DBN) and diazabicycloundecene (DBU).

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing ge uses standard methods.

The inventive method (G) is characterized in that Ver bonds of the formulas (I-1-a) to (I-3-a) each with sulfonic acid chlorides of For  mel (IX) optionally in the presence of a diluent and given if necessary in the presence of an acid binder.

In the production process (G), the per mole of starting compound Formula (I-1-a) to (I-3-a) about 1 mol of sulfonic acid chloride of formula (IX) at -20 to 150 ° C, preferably at 0 to 70 ° C.

Process (G) is preferably carried out in the presence of a diluent carried out.

All inert polar organic solvents can be used as diluents Question like ethers, amides, ketones, carboxylic acid esters, nitriles, sulfones, sulfoxides or halogenated hydrocarbons such as methylene chloride.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, Ethyl acetate, methylene chloride used.

Is made in a preferred embodiment by adding strong Deprotonating agents (such as sodium hydride or potassium tertiary butoxide) Enolate salt of the compounds (I-1-a) to (I-3-a), can on the further addition acid binders can be dispensed with.

If acid binders are used, the usual inorganic or organic compounds are used bases in question, examples include sodium hydroxide, sodium carbonate, Potassium carbonate, pyridine and triethylamine listed.

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing ge uses standard methods.  

Process (H) according to the invention is characterized in that Compounds of formulas (I-1-a) to (I-3-a) each with phosphorus compounds of formula (X) optionally in the presence of a diluent and if appropriate in the presence of an acid binder.

The manufacturing process (H) uses to obtain compounds Formulas (I-1-e) to (I-3-e) to 1 mol of the compounds (I-1-a) to (I-3-a), 1 to 2, preferably 1 to 1.3 moles of the phosphorus compound of the formula (X) at Tempe temperatures between -40 ° C and 150 ° C, preferably between -10 and 110 ° C.

Process (H) is preferably carried out in the presence of a diluent carried out.

All inert, polar organic solvents can be used as diluents Question like ethers, carboxylic acid esters, halogenated hydrocarbons, ketones, Amides, nitriles, sulfones, sulfoxides etc.

Acetonitrile, dimethyl sulfoxide, tetrahydrofuran, dimethyl are preferred formamide, methylene chloride used.

Conventional inorganic or organic bases in question such as hydroxides, carbonates or amines. Exemplary be sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethyl amine listed.

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing ge uses the usual methods of organic chemistry. The end products who preferably by crystallization, chromatographic purification or by  so-called "distillation", i.e. H. Removal of volatile components in the Va vacuum cleaned.

Process (I) is characterized in that compounds of the formulas (I-1-a) to (I-3-a) each with metal hydroxides or metal alkoxides of the formula (XI) or amines of the formula (XII), optionally in the presence of a diluent means implemented.

Preferred diluents in process (I) according to the invention as ethers such as tetrahydrofuran, dioxane, diethyl ether or alcohols such as Methanol, ethanol, isopropanol, but also water can be used. That invented Process (I) according to the invention is generally carried out under normal pressure. The reaction temperature is generally between -20 ° C and 100 ° C, preferably between 0 ° C and 50 ° C.

Process (J) according to the invention is characterized in that Compounds of formulas (I-1-a) to (I-3-a) each with (Jα) compounds of Formula (XIII) optionally in the presence of a diluent and counter optionally in the presence of a catalyst or (Jα) with compounds of the formula (XIV) if appropriate in the presence of a diluent and if appropriate reacted in the presence of an acid binder.

In production process (Jα), the per mole of starting compound Formulas (I-1-a) to (I-3-a) approx. 1 mol isocyanate of the formula (XIII) at 0 to 100 ° C, preferably at 20 to 50 ° C.

Process (Jα) is preferably carried out in the presence of a diluent carried out.  

All inert organic solvents are suitable as diluents, such as aromatic hydrocarbons, halogenated hydrocarbons, ethers, Amides, nitriles, sulfones or sulfoxides.

If necessary, catalysts can be added to accelerate the reaction will. As catalysts, organotin compounds, such as B. Dibutyltin dilaurate can be used.

It is preferably carried out at normal pressure.

In the production process (Jβ), the per mole of starting compound Formulas (I-1-a) to (I-3-a) approx. 1 mol of carbamic acid chloride of the formula (XIV) 0 to 150 ° C, preferably at 20 to 70 ° C.

All inert polar come as optionally added diluents organic solvents in question such as ethers, carboxylic acid esters, nitriles, ketones, Amides, sulfones, sulfoxides or halogenated hydrocarbons.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or Methylene chloride used.

Is made in a preferred embodiment by adding strong Depro toning agents (such as sodium hydride or potassium tert-butylate) the enolate salt of the compound (I-1-a) to (I-3-a), can on the further addition of Acid binders can be dispensed with.

If acid binders are used, common inorganic or organic compounds are used African bases in question, examples include sodium hydroxide, sodium carbonate, Potassium carbonate, triethylamine or pyridine called.  

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing ge uses standard methods.

The active substances are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:
From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus
From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.
From the order of the Symphyla z. B. Scutigerella immaculata.
From the order of the Thysanura z. B. Lepisma saccharina.
From the order of the Collembola z. B. Onychiurus armatus.
From the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Reticulitermes spp.
From the order of the Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.
From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.
From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodaliphasumum., Phorodaliphasum bilobatus, Nephotettix cincticeps, Lecanium corni, Sais setia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.
From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplocapsia n. , Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnidana, Homona magnidana.
From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysoceppus, st spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus sppium, sides., Nipt ., Tenebrio molitor, Agriotes spp., Cono derus spp., Melolontha melolontha, Amphimallon solsti tialis, Costelytra zealandica.
From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomox ., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.
From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.
From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Choroptes spp.,. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The active compounds according to the invention are notable for high insecticidal and acaricidal effectiveness.

They can be used to control plants with particularly good success harmful insects, such as against the larvae of horseradish leaf beetle (Phaedon cochleariae) or against the larvae of the green rice leafhopper (Nepho  tettix cincticeps) and against the caterpillars of the cockroach (Plutella maculipennis) deploy.

The active compounds according to the invention can also be used as defoliants, desiccants, Herbicides and especially used as weed killers will. Weeds in the broadest sense are understood to mean all plants that are on Growing up in places where they are undesirable. Whether the substances according to the invention as total or selective herbicides act depends essentially on the averted crowd.

The dosages of the inventive weed control necessary Active substances are between 0.001 and 10 kg / ha, preferably between 0.005 and 5 kg / ha.

The active compounds according to the invention can, for. B. ver used in the following plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotola, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cycnodon, Monochoria, Fimbristylis, Sagittaria, Iuspasumumumisumumum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Sachharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means limited to limited to these genera, but also extends in the same way other plants.

The compounds are suitable depending on the concentration Total weed control e.g. B. on industrial and track systems and on paths and Places with and without tree cover. Likewise, the connections to Weed control in permanent crops, e.g. B. forest, ornamental trees, fruit, wine, Citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hops, on ornamental and sports turf and pastures and for selective Weed control can be used in annual crops.

The active compounds according to the invention are very suitable for selective control monocotyledon weeds in dicotyledon crops before and after. she can be used for example in cotton or sugar beet with very good success Control of harmful grass can be used.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated nated natural and synthetic substances as well as very fine encapsulation in polymers Fabrics.  

These formulations are prepared in a known manner, e.g. B. by Ver mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally using surface-active agents Agents, that is emulsifiers and / or dispersants and / or foam generators resources.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylene or methylene chloride, aliphatic coal water serstoffe, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and their ethers and esters, Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and Water.

The following are suitable as solid carriers:
e.g. B. ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam-generating agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersing agents come into question: z. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxym 36793 00070 552 001000280000000200012000285913668200040 0002019651686 00004 36674ethyl cellulose, ver natural and synthetic polymers in powder, granular or latex form be used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids such as cephalins and lecithins and synthetic phos pholipid. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, Copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight. Active ingredient, preferably between 0.5 and 90% and also preferred Extenders and / or surfactants.

The active ingredient according to the invention can be in its commercially available formulations as well as in the application forms prepared from these formulations in Mi with other active ingredients, such as insecticides, attractants, sterilants, Acaricides, nematicides, fungicides, growth regulators or Her are bicidal. Insecticides include, for example, phosphoric acid esters, Carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms u. a.

Particularly cheap mixing partners are e.g. B. the following:

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-di chloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cuftaneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Fuberilafil, Fuberri Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifen thrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlor fluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocy thrin, Chrinophhrin, Clophin Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho prophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Iver mectin, Lambda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin Monocrotophos, Moxidectin,
Naled, NC 184, NI 25, Nitenpyram,
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Teme phos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhronononium, Tralomenhronon, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomenhrononium, Tronomeno
Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

Herbicides

for example anilides, such as. B. Diflufenican and Propanil; Aryl carboxylic acids, such as e.g. B. dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, such as. B. 2.4 D, 2.4 DB, 2.4 DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy phenoxy-alkanoic acid esters, such as. B. Diclofop-methyl, fenoxaprop-ethyl, fluazifop butyl, haloxyfop-methyl and quizalofop-ethyl; Azinones, such as B. Chloridazon and norflurazon; Carbamates, e.g. B. chlorpropham, Desmedipham, Phenmedipham and Propham; Chloroacetanilides such as e.g. B. alachlor, acetochlor, Butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Dinitroaniline, such as B. Oryzalin, Pendimethalin and Trifluralin; Diphenyl ether, such as. B. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen and Oxy fluorfen; Ureas, such as B. chlorotoluron, diuron, fluometuron, isoproturon, Linuron and methabenzthiazuron; Hydroxylamines, such as. B. alloxydim, Clethodim, Cycloxydim, Sethoxydim and Tralkoxydim; Imidazolinones, e.g. B. Imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles such as B. bromine oxynil, dichlobenil and ioxynil; Oxyacetamides such as e.g. B. Mefenacet; Sulfonyl ureas, such as B. amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, Chlorsulfuron, Cinosulfuron, Metsulfuron-methyl, Nicosulfuron, Primisulfuron, Pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates such as e.g. B. butylates, cycloates, dialallates, EPTC, Esprocarb, Molinate, Prosulfocarb, Thiobencarb and Triallate; Triazines, e.g. B. atrazine, Cyanazin, simazin, simetryne, terbutryne and terbutylazin; Triazinones such as e.g. B. Hexazinone, metamitron and metribuzin; Others, such as B. aminotriazole, Benfuresate, Bentazone, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.

The active ingredient according to the invention can also be in its commercially available form formulations and in the application forms prepared from these formulations in a mixture with synergists. Synergists are connections through which the effect of the active ingredients is increased without the added synergist must be actively active itself.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary widely. The drug concentration the use forms can be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms Wise.

When used against hygiene and storage pests, the stands out Active ingredient through an excellent residual effect on wood and clay as well due to good stability to alkali on limed substrates.

The active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas. These parasites include:
From the order of the Anoplurida z. B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
From the order of the Mallophagida and the subordinates Amblycerina and Ischnocerina z. B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
From the order Diptera and the subordinates Nematocerina and Brachycerina z. B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp ., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.
From the order of the Siphonapterida z. B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
From the order of the Heteropterida z. B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order of the Blattarida z. B. Blatta orientalis, Periplaneta americana Blattela germanica, Supella spp.
From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata z. B. Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysaiis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp. Pneu monyssus spp., Sternostoma spp., Varroa spp.
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) z. B. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp. Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

The active compounds of the formula (I) according to the invention are also suitable for combating treatment of arthropods, the farm animals, such as. B. cattle, sheep, Goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, Ducks, geese, bees, other pets such as B. dogs, cats, house birds, Aquarium fish and so-called experimental animals, such as. B. hamsters, guinea pigs infested rats, rats and mice. By fighting these arthropods deaths and reduced performance (meat, milk, wool, skins, Eggs, honey, etc.) can be reduced, so that the use of the inventive more active and more economical animal husbandry is possible.

The active compounds according to the invention are used in the veterinary sector in known manner by enteral administration in the form of, for example, Tab Latvian, capsules, watering, drenching, granules, pastes, boluses, feed-through Method, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), Implants, by nasal application, by dermal application in the form for example diving or bathing (dipping), spraying (spray), pouring on (Pour-on and spot-on), washing, powdering and with the help of molded articles containing active ingredients, such as collars, ear tags, tail tags, Limb straps, holsters, marking devices etc.

When used for cattle, poultry, pets etc. you can use the active ingredients of the formula (I) as formulations (for example powders, emulsions, flowable Agents), which contain the active ingredients in an amount of 1 to 80 wt .-%, directly  or after 100 to 10,000 times dilution or as chemical Use bath.

It has also been found that the compounds of the formula (I) show a high insecticidal activity against insects, the technical mate destroy rialien.

The following insects may be mentioned by way of example and preferably, but without limitation:
Beetle like
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubis linearis, Lyctus pubis linearis, speculum Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.
Skin wings like
Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.
Termites like
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes fiavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes dar winiensis, Zootermopsis nevadensis, Coptotermes formosanus.
Bristle tails like
Lepisma saccharina.

In the present context, technical materials include non-living ones To understand materials, such as preferably plastics, adhesives, glues, Pa paper and cardboard, leather, wood and wood processing products and painting medium.

It is very particularly preferred to protect against insect attack material around wood and wood processing products.

Among wood and wood processing products, which by the invention Agents or mixtures containing them can be protected is exemplary to understand: timber, wooden beams, railway sleepers, bridge parts, jetties, Wooden vehicles, boxes, pallets, containers, telephone poles, wooden panels, Wooden windows and doors, plywood, chipboard, carpentry or wood pro products that are used in general in house construction or in joinery Find.

The active ingredients can be used as such, in the form of concentrates or in general usual formulations such as powders, granules, solutions, suspensions, emul sions or pastes.

The formulations mentioned can be prepared in a manner known per se be, e.g. B. by mixing the active ingredients with at least one solution or diluent, emulsifier, dispersing and / or binding or fixing agent tels, water repellants, possibly desiccants and UV stabilizers and opp if necessary dyes and pigments and other processing aids.

The insecticidal agents used to protect wood and wood-based materials or concentrates contain the active ingredient according to the invention in a concentra tration from 0.0001 to 95 wt .-%, in particular 0.001 to 60 wt .-%.  

The amount of agents or concentrates used depends on the type and type come from insects and depending on the medium. The optimal amount to use can be determined by test series in the application. Generally in my opinion, however, it is sufficient 0.0001 to 20% by weight, preferably 0.001 to 10 wt .-%, of the active ingredient, based on the material to be protected.

An organic chemical solvent serves as the solvent and / or diluent solvent or solvent mixture and / or an oily or oily heavy volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agent.

The organic chemical solvents used are preferably oily or oily ones Solvents with an evaporation number above 35 and a flash point above half 30 ° C, preferably above 45 ° C, used. As such volatile, water-insoluble, oily and oily solvents become corresponding mine ralöle or their aromatic fractions or mineral oil-containing solvent mixtures cal, preferably white spirit, petroleum and / or alkylbenzene used.

Mineral oils with a boiling range of 170 to 220 ° C are advantageous, test petrol with a boiling range of 170 to 220 ° C, spindle oil with a boil range from 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 up to 280 ° C, turpentine oil and the like.

In a preferred embodiment, liquid aliphatic hydrocarbons substances with a boiling range of 180 to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 220 ° C and / or locker oil and / or monochloronaphthalene, preferably - Monochloronaphthalene used.  

The organic non-volatile oily or oily solvents with a Evaporation rate above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partly due to slightly or medium-volatile organic chemistry cal solvents are replaced, with the proviso that the solvent mix also an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide fungicide Mixture is soluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, part of the organic chemical Solvent or solvent mixture through an aliphatic polar orga niche chemical solvent or solvent mixture replaced. Preferably come alipha containing hydroxyl and / or ester and / or ether groups organic chemical solvents such as glycol ether, esters or the like for use.

As an organic chemical binder in the present Er finding the known water-dilutable and / or in the used organic chemical solvents soluble or dispersing or emul gable synthetic resins and / or binding drying oils, especially binders consisting of or containing an acrylic resin, a vinyl resin, e.g. B. polyvinyl acetate, Polyester resin, polycondensation or polyaddition resin, polyurethane resin, Alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as Inden-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or Resin used.

The synthetic resin used as a binder can be in the form of an emulsion, disper sion or solution. Bitumen or bituminous substances up to 10 wt .-%, are used. In addition, you can  dyes, pigments, water-repellants, odor correctors known per se tien and inhibitors or corrosion protection agents and the like. Be used.

According to the invention, preference is given to at least one organic chemical binder an alkyd resin or modified alkyd resin and / or a drying vegetable Contain oil in the medium or in the concentrate. Are preferred according to the Invention alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight.

The binder mentioned can be wholly or partly by a fixation medium (mixture) or a plasticizer (mixture) can be replaced. These additions should len volatilization of the active ingredients and crystallization or precipitators prevent. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

The plasticizers come from the chemical classes of phthalic acid esters such as Dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight Gly kolether, glycerol ester and p-toluenesulfonic acid ester.

Fixing agents are chemically based on polyvinyl alkyl ethers such as. B. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.

Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above-mentioned orga nisch-chemical solvents or diluents, emulsifiers and dispersers gators.  

A particularly effective wood protection is provided by industrial impregnation drive, e.g. B. vacuum, double vacuum or printing process.

The ready-to-use agents can, if appropriate, still further insecticidal and optionally contain one or more fungicides.

The additional mixing partners are preferably those in WO 94/29 268 Insecticides and fungicides mentioned in question. The ones mentioned in this document Connections are an integral part of this application.

Insecticides such as chlorine are particularly preferred as admixing partners pyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, delta methrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and tri flumuron, and fungicides such as epoxyconazole, hexaconazole, azaconazole, Propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlor fluanide, tolylfluanid, 3-iodo-2-propynyl butyl carbamate, N-octyl-isothiazole in-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

The manufacture and use of the active compounds according to the invention start out the following examples.  

Examples Example I-1-a-1

To 14.05 g (0.125 mol) of potassium tert-butoxide in 54 ml of absolute tetrahydrofuran (THF) is added dropwise at reflux temperature 17.3 g of the compound according to Example II-1 in 160 ml of absolute toluene and stirred for a further 1.5 hours at this temperature. After after cooling, 160 ml of water are added, the phases are separated and the toluene is extracted phase with 80 ml of water and acidifies the combined aqueous phases at 0 to 20 ° C. with concentrated HCl. The product is suctioned off, washed, dried and stirred for further cleaning with methyl tert-butyl (MTB) ether / n-hexane, sucks off and dries. Yield: 12.1 g (77% of theory), mp: 200 ° C.

Analogously or according to the general information on the preparation, the following are obtained the compounds of the formula (I-1-a):

Table 4

Example (I-1-b-1)

2.88 g (0.010 mol) of the compound according to Example (I-1-a-1) and 2.1 ml (15 mmol) Triethylamine in 50 ml of anhydrous ethyl acetate are refluxed with 1.85 ml (0.15 mol) of pivaloyl chloride in 5 ml of anhydrous ethyl acetate transferred. The mixture is stirred under reflux until the reaction after thin layer chromatography graphic control has ended. For working up, the approach is concentrated in Methylene chloride added, washed twice with 50 ml of 0.5 N sodium hydroxide solution, dried over magnesium sulfate and evaporated. The raw product is made MTB ether / n-hexane recrystallized. Yield: 2.0 g (53% of theory), mp: 193 ° C.

Analogously or according to the general information on the preparation, the fol compounds of the formula (I-b-I):  

Table 5

Example (I-1-c-1)

To 2.88 g (0.010 mol) of the compound according to Example (I-1-a-1) and 1.4 ml (0.010 mol) of triethylamine in 50 ml of anhydrous CH ₂ Cl _{2 are added} dropwise at 0 to 10 ° C. 1, 0 ml (0.010 mol) of chloroformate in 5 ml of anhydrous methylene chloride and stirred at room temperature until the reaction is complete after a thin layer chromatographic check. For working up, it is washed twice with 50 ml of 0.5 N sodium hydroxide solution, dried over magnesium sulfate and evaporated. Yield: 2.8 g (77% of theory), mp: 157 ° C.

Analogously or according to the general information on the preparation, the following compounds of formula (I-1-c):

Table 6

Example II-1

Concentrated to 51.3 g (0.513 mol). Sulfuric acid is carefully added dropwise at 30 to 40 ° C 29.1 g (0.1016 mol) of the compound according to Example (XXV-1) in 310 ml of water free methylene chloride and stirred for 2 hours at this temperature. Then drips you add 69 ml of absolute methanol so that an internal temperature of about Set 40 ° C and stir for 6 hours at 40 to 70 ° C.  

For working up, pour onto 0.51 kg of ice, extracted with methylene chloride, washes with aqueous sodium bicarbonate solution, dries and evaporates. The residue is recrystallized from methyl tert-butyl ether / n-hexane. Off Loot: 17.3 g (53% of theory), mp: 168 ° C.

Analogous to example (II-1) and according to the general information on the preparation the following compounds of formula (II) are prepared.

Table 7

Example XXV-1

To 15.8 g of 3-aminotetrahydropyran-3-carbonitrile (according to Example XXIV) and 17.6 ml of triethylamine in 250 ml of absolute THF are added dropwise at 0 to 10 ° C. 25 g Mesitylene acetic acid chloride in 30 ml of absolute THF and stir until the reaction is finished. The mixture is poured into a mixture of 500 ml ice water and 200 ml 1N HCl stirred in. It is suctioned off, the residue is taken up in methylene chloride and dried and constricts. Yield 29.1 g (81% of theory), mp. 153 ° C.

Analogous to example (XXV-I) or according to the general information on the production the following compounds of formula (XXV) are prepared:  

Table 8

Example I-2-a-1

18.1 g (0.057 mol) of the compound according to Example III-1 in 30 ml of dry Bimethylformamide (DMF) is slowly added dropwise to 9.58 g (0.085 mol) at 10 ° C.  Potassium tert-butoxide in 10 ml dry DMF and stir overnight in room temperature. The DMF is distilled off, the residue is taken up in 1 l of water and slowly acidified with concentrated HCl. You vacuum, wash with water and dries in vacuo at 50 ° C. Mp 261 ° C.

Example (I-2-a-2)

Analogously to Example I-2-a-1, the compound is obtained starting from the compound according to Example (III-2)

Mp 266-269 ° C.

Example (III-1)

10 g (0.057 mol) of the compound according to Example (XXVI) and 11.3 g of 2,4,6-trimethylphenyl-acetic acid chloride are heated to 140 ° C. for 6 hours and then degassed.
Yield 18.1 g of an oil, mass spectrum (MS) (m / e): 334 (M⁺, 36%), 160 (38%), 133 (100%).

Example (III-2)

The compound is obtained analogously to Example (III-1)

as an oil.

Example XXIV

To the mixture of 222.4 g (3.27 mol) 25% ammonia solution, 75 g (1.4 mol) Ammonium chloride, 68.7 g (1.4 mol) sodium cyanide and 210 ml water are added dropwise at room temperature 116.8 g (1.17 mol) 3-oxa-cyclohexanone-1 (see Bull. Soc. Chim. Fr. (1970), (10), 3521-3) and stirred overnight at 45 ° C. After extraction with Methylene chloride was obtained 95.2 g (64% of theory), the one shown above Compound that without further purification in the preparation of the compounds of the Formula XXV was used.  

Example (XXVI)

The mixture of 89.3 g (0.7 mol) of the compound, according to Example (XXVIa) in 420 ml of ethanol is saturated with HCl at 0 to -20 ° C. Stir for another hour 0 ° C and then allows to come to room temperature within about 3 hours.

Excess HCl is removed in vacuo, then it is concentrated. The residue is mixed with 400 ml of cold water and stirred for 1 hour. It is extracted twice with methylene chloride, dried and concentrated.
Yield 90 g, bp. _0.06 66 ° C.

Example (XXV1a)

To 85.0 g (0.85 mol) of 3-oxa-cyclohexanone-1 (Bull. Soc. Chlm. Fr. (1970) (10), 3521-3) and 0.72 ml of triethylamine are added dropwise at room temperature 24. 3 g (0.9 mol) of hydrocyanic acid and stirred for a further 1.5 hours at room temperature. It is stabilized with 0, 12 ml of o-phosphoric acid and degassed in a water jet vacuum.
Yield: 102 g (94% of theory)

Examples of use Example A Myzus test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water to the desired one Concentration.

Cabbage leaves (Brassica oleracea), heavily from the peach aphid (Myzus persicae) are infested, by dipping into the active ingredient preparation of the desired Concentration treated.

After the desired period of time, the destruction in% is determined. Here means 100% that all aphids have been killed; 0% means that there are no aphids were killed.

In this test, e.g. B. the compounds according to the preparation examples (I-1-a-2), (I-1-a-3), (I-1-b-2) and (I-1-c-1) at an exemplary drug concentration tration of 0.1%, killing of 100% after 6 days.  

Example B Nephotettix test

Solvent: 20 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water to the desired one Concentration.

Rice seedlings (Oryzae sativa) are immersed in the active ingredient preparation desired concentration and treated with the green rice leafhopper (Nephotettix cincticeps) when the seedlings are still moist.

After the desired time, the kill is determined in%. 100% means that all cicadas have been killed; 0% means that no cicadas are killed were.

In this test, e.g. B. the compounds according to the preparation examples (I-1-a-1), (I-1-a-2), (I-1-a-3), (I-1-b-1), (I-1-b-2), (I-1-b-3), (I-1-b-4), (I-1-b-5) and (I-1-c-3) at an exemplary active ingredient concentration of 0.1%, killing from 100% after 6 days.  

Example C Phaedon larval test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water to the desired one Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with larvae of the horseradish beetle (Phaedon cochleariae) occupied while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae are killed were.

In this test, e.g. B. the compounds according to the preparation examples (I-1-a-1), (I-1-a-2), (I-1-a-3), (I-1-b-1), (I-1-b-2), (I-1-b-3), (I-1-b-4), (I-1-b-5) and (I-1-c-1) at an exemplary active ingredient concentration of 0.1%, killing from 100% after 7 days.  

Example D Spodoptcra frugiperda test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water to the desired one Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars of the owl butterfly Spodoptera frugiperda) occupied while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars are killed were.

In this test, e.g. B. the compounds according to the preparation examples (I-1-b-4) and (I-1-c-1) at an exemplary active ingredient concentration of 0.1% 100% kill after 7 days.  

Example E Tetranychus test (OP-resistant / immersion treatment)

Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water to the desired one Concentration.

Bean plants (Phaseolus vulgaris), strongly of all stages of the common Spider mite Tetranychus urticae are infected in a drug preparation desired concentration immersed.

After the desired time, the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites are removed were killed.

In this test, e.g. B. the compounds according to the preparation examples (I-1-a-1), (I-1-b-1), (I-1-b-2) and (I-1-c-1) at an exemplary drug concentration tration of 0.1%, killing of 100% after 13 days.

Claims (14)

1. Compounds of formula (I)
in which
V represents hydrogen, halogen, alkyl or alkoxy,
W represents hydrogen cyano, nitro, halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy, in each case optionally substituted phenyl, phenoxy, phenylthio, phenylalkoxy or phenylalkylthio,
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy, cyano, nitro, in each case optionally substituted phenyl, phenoxy, phenylthio, phenylalkyloxy or phenylalkylthio,
Y represents hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, cyano or nitro,
Z represents hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, hydroxy, cyano, nitro or in each case optionally substituted phenoxy, phenylthio, 5- or 6-membered hetaryloxy, 5- or 6-membered hetarylthio, phenylalkyloxy or phenylalkyltbio, or
Y and Z together with the carbon atoms to which they are attached represent an optionally substituted cycle which is optionally interrupted by one or more heteroatoms, or
W and Z together with the carbon atoms to which they are attached represent an optionally substituted cycle which may be interrupted by one or more heteroatoms,
Het for one of the groups
stands,
wherein
G for hydrogen (a) or for one of the groups
stands,
wherein
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R ^{1 represents} in each case optionally substituted by halogen or cyano substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl or for cycloalkyl or heterocyclyl optionally substituted by halogen, alkyl or alkoxy or for optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryl oxyalkyl ,
R ² represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, each optionally substituted by halogen or cyano, or represents optionally substituted cycloalkyl, phenyl or benzyl,
R ³ , R ⁴ and R ⁵ independently of one another each represent optionally substituted by halogen substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenyltbio or cycloalkylthio or for optionally substituted phenyl, benzyl, phenoxy or phenylthio,
R ⁶ and R ⁷ independently of one another represent hydrogen for each optionally substituted by halogen or cyano substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, each optionally substituted phenyl or benzyl, or together with the N atom to which they are attached, form an optionally oxygen or sulfur-containing and optionally substituted cycle. 2. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

• (A) compounds of the formula (I-1-a)
  in which
  V, W, X, Y and Z have the meanings given in claim 1,
  receives,
  if
  Compounds of formula (II)
  in which
  V, W, X, Y and Z have the meanings given above,
  and
  R ^{8 represents} alkyl,
  intramolecularly condensed in the presence of a diluent and in the presence of a base,
• (B) compounds of the formula (I-2-a)
  in which
  V, W, X, Y and Z have the meanings given above,
  get when one
  Compounds of formula (III)
  in which
  V, W, X, Y, Z and R ^{8 have} the meanings given above,
  intramolecularly condensed in the presence of a diluent and in the presence of a base,
• (C) compounds of the formula (I-3-a)
  in which
  V, W, X, Y and Z have the meanings given above,
  get when one
  Compounds of formula (IV)
  in which
  V, W, X, Y, Z and R ^{8 have} the meanings given above and
  T represents hydrogen, halogen, alkyl or alkoxy,
  optionally cyclized intramolecularly in the presence of a diluent and in the presence of an acid,
  and then, if appropriate, the compounds of the formulas (I-1-a) to (I-3-a) obtained in this way, in which V, W, X, Y and Z have the meanings given above, in each case
• (D) α) with acid halides of the formula (V)
  in which
  R ^{1 has} the meaning given in Claim 1 and Hal represents halogen
  or
  β) with carboxylic anhydrides of the formula (VI) R ¹ -CO-O-CO-R ¹ (VI) in which
  R ^{1 has} the meaning given above,
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid binder; or
• (E) with chloroformate or chloroformate thioester of the formula (VII) R ² -M-CO-Cl (VII) in which
  R ² and M have the meanings given above,
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid binder;
• (F) with chloromothio formic acid esters or chlorodithio formic acid esters of the formula (VIII)
  in which
  M and R ^{2 have} the meanings given in claim 1,
  if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid binder,
  or
• (G) with sulfonic acid chlorides of the formula (IX) R ³ -SO ₂ -Cl (IX) in which
  R ^{3 has} the meaning given in claim 1,
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid binder; or
• (H) with phosphorus compounds of the formula (X)
  in which
  L, R ⁴ and R ^{5 have} the meanings given in claim 1 and
  Hal stands for halogen,
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid binder; or
• (I) with metal compounds or amines of the formulas (XI) or (XII)
  in which
  Me for a monovalent or divalent metal
  t for the number 1 or 2 and
  R ¹⁰ , R ¹¹ , R ¹² independently of one another represent hydrogen or alkyl,
  if appropriate in the presence of a diluent,
  or
• (J) α) with isocyanates or isothiocyanates of the formula (XIII) R ⁶ -N = C = L (XIII) in which
  R ⁶ and L have the meanings given in Claim 1,
  if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst or
  β) with carbamic acid chlorides or thiocarbamic acid chlorides of the formula (XIV)
  in which
  L, R ⁶ and R ^{7 have} the meanings given in Claim 1,
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid binder.

3. Compounds of formula (II)
in which
V, W, X, Y and Z have the meanings given in claim 1 and
R ^{8 represents} alkyl. 4. Compounds of formula (XVII)
in which
V, W, X, Y and Z have the meanings given in claim 1. 5. Compounds of the formula (XXV)
in which
V, W, X, Y and Z have the meanings given above and 6. Compounds of formula (III)
in which
V, W, X, Y and Z have the meanings given above and
R ^{8 represents} alkyl. 7. Compounds of the formula (XXVI)
in which
R ^{8 represents} alkyl. 8. Compounds of formula (IV)
in which
T, V, W, X, Y and Z have the meanings given above and
R ^{8 represents} alkyl. 9. Compounds of the formula (XXVII)
in which
T represents hydrogen, halogen, alkyl or alkoxy and
Hal stands for halogen. 10. Compound of formula (XXIV)
11. pesticides or herbicides, characterized by a content of a compound of formula (I) according to claim 1. 12. Use of compounds of formula (I) according to claim 1 for Control of pests and weeds. 13. A method of controlling pests and weeds, thereby characterized in that compounds of formula (I) according to claim 1 Pests or weeds and / or their habitat. 14. Process for the preparation of pesticides and herbicides Agents, characterized in that compounds of the formula (I) according to claim 1 with extenders and / or surface-active agents mixed.